2019
DOI: 10.1021/jacs.9b10689
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Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

Abstract: Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and twoelectron pathways, hence providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dim… Show more

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Cited by 44 publications
(26 citation statements)
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“…[102] The Ni-catalyzed reaction of [1.1.1]propellane 70 as a carbene precursor with 4-ethynylbiphenyl 71 produced 72, presumably through enyne metathesis (Scheme 28). [103] Analogous reaction with alkenes led to cyclopropanation.…”
Section: Nickelmentioning
confidence: 99%
“…[102] The Ni-catalyzed reaction of [1.1.1]propellane 70 as a carbene precursor with 4-ethynylbiphenyl 71 produced 72, presumably through enyne metathesis (Scheme 28). [103] Analogous reaction with alkenes led to cyclopropanation.…”
Section: Nickelmentioning
confidence: 99%
“…The reactions of 1 with cations is an underexplored eld; despite the observation of rapid protonation by acetic acid, 30 few cationpromoted reactions have been reported. 31,32 Cationic bicyclo [1.1.1]pentyl adducts are known to rapidly fragment to bicyclo [1.1.0]butyl-1-carbinyl cations (Fig. 7a), 76 which suggests that a signicant change in the electronics of the cage occurs as addition takes place.…”
Section: The Reactivity Of [111]propellane With Cationsmentioning
confidence: 99%
“…A third reactivity mode of 1 involves facile cationic addition, a process that fragments the cage to an exo-methylene cyclobutane. [30][31][32] This diverse 'omniphilic' reactivity has traditionally been ascribed to the high strain energy of [1.1.1]propellane (total strain energy $100 kcal mol À1 ), 33 albeit only $30 kcal mol À1 of this strain is thought to be released on cleavage of the interbridgehead C1-C3 bond. 2,34 Nonetheless, this omniphilicity is not generally observed with other ring-opening reactions where relief of ring strain is a driving force (such as in cyclopropane, E strain ¼ $28 kcal mol À1 ), 35 which could suggest other factors govern the reactivity of 1.…”
Section: Introductionmentioning
confidence: 99%
“…61 − 63 Some alternative methods for the synthesis of cyclopropanes involve the use of different types of ylides, 64 67 free dihalocarbenes, 68 direct cyclizations, 69 , 70 ring contractions, 71 73 radical pathways, 74 77 or the Kulinkovich reaction, 78 80 among others. 81 84 …”
Section: Introductionmentioning
confidence: 99%